Substituted iminopyrrolines and iminopyrrolidines



United States Patent This invention is concerned with specific substituted iminopyrrolines and irninopyrrolidines, as well as the acid addition salts thereof, as new compositions of matter. It also deals with methods for the preparation of the specific substituted iminopyrrolines and iminopyrrolidines. The compounds of this invention may be represented by the formulas:

A a a R :NR

and

Actually, when R equals hydrogen, the compound represented by Formula B is to varying degrees, according principally to reaction conditions and the values of R, R R R and R in t-autorneric relationship with the compounds having the following structures:

It is highly probable, based on the best experimental and analytical evidence, that the predominant tautomeric product is that of Formula D, but appreciable amounts of C and B are undoubtezfly present. In the present sense, Formula 13 will be referred to as the principal form of the three possible tautomeric structures (B, C, and D), but such a reference is meant to include the other two (C and D) tautomeric for-ms. Furthermore, when R represents an alky group within the definition, to be more fully explained hereinafter, there exists in various appreciable amounts the compound having the structure:

wherein R is an alkyl group of l to 9 carbon atoms, including cycloalkyl, or hydrogen.

The symbol R represents hydrocarbon groups of l to 10 carbon atoms, preferably alkyl, aralkyl, cycloalkyl,

aiaets Ratented Nov. 5, 1963 "ice aryl and alkaryl. The symbol R represents a hydrogen atom or an alkyl group of l to 4 carbon atoms. The symbols R and R may be a hydrogen atom or hydrocarbon groups containing irorn l to 10 carbon atoms, including alkyl, aralkyl, cyoloallcyl, aryl and allraryl groups. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing 5 to 6 carbon atoms which in turn may have alkyl substituents containing a total of no more than 4 additional carbon atoms. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing 5 to 6 carbon atoms which in turn may have 'alkyl substituents containing a total of no more than four additional carbon atoms. In addition, R and R taken together with the carbon atoms to which they are joined may form a canbocyclic ring containing 5 to 6 carbon atoms which in turn may have alkyl substituents containing a total of no more than 4 additional carbon atoms. The total number of carbon atoms in the cyanolretone should not exceed 24. The preferred embodiments are those in which R and R are alkyl groups, R is a hydrogen atom, and R is a methyl group. R R and R may typically individually represent methyl, butyl, octyl, ibenzyl, phenylbutyl, cycl1opentyl, cyclohexyl, phenyl, naphthyl, rbutylphenyl groups, and the like.

Each of the symbols R and R represent a hydrogen atom, an alkyl group of l to 18 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, an aryl group of up to 10 carbon atoms, an aral'kyl group of up to 18 carbon atoms, an alkarylalkyl group of up to 30 carbon atoms, an alkoxyalkyl group of 3 to-24 carbon atoms, a hydroxyalkyl group of 2 to 12 carbon atoms, and an alkylaminoalkyl group of 3 to 18 carbon atoms provided that the amino group is a secondary or tertiary structure, that is non-primary. Alkyl, in the above definition, is to be construed to include 'cycloalkyl and alkylcyoloalkyl within the range of carbon atoms previously set forth. It is preferred that R and R represent the same groups within any single product.

Typical R and R representations are hydrogen, methyl, ethyl, butyl, octyl, decyl, dodecyl, octadecyl, cycloentyl, cyclohexyl, butylcyclohexyl, octylcyclohexyl, butylcyclohexylethyl, propenyl, butenyl, hexenyl, ootenyl, decenyl, dodecenyl, octadecenyl, phenyl, naphthyl, benzyl, phenylethyl, phenylbutyl, phenyldodecyl, methylphenyl, ethylphenyl, butylphenyl, octylphenyl, .nonylphenyl, decylphenyl, hexadecylphenyl, octadecylphenyl, methylbenzyl, ethylbenzyl, butylbenzyl, octylbenzyl, dodecylbenzyl, butylphenylbutyl, octylphenylethyl, dioctylphenyleth l, dodecylphenyloctyl, methoxyethyl, methoxypropyl, methoxyhexyl, methoxydecyl, methoxyoct-adecyl, ethoroethyl, ethoxybutyl, ethoxyoctyl, ethoxydodecyl, propoxyethyl, propoxybutyl, propoxyheptyl, propoxytetradecyl, butoxyethyl, butoxybutyl, butoxyoctyl, butoxydodecyl, butoxyootadecyl, pentoxyethyl, pentoxybutyl, pentoxydecyl, hexoxyethyl, hexoxyhexyl, hexoxydodecyl, hexoxyoctadecyl, heptoxyethyl, heptoxyoctyl, octoxyethyl, octoxybutyl, octoxyoctyl, octoxydodecyl, nonoxypropyl, nonoxyheptyl, nonoxytridecyl, decoxyethyl, decoXyocty-l, undecoxybutyl, dodecoxypropyl, dodecoxydecyl, dodecoxydodecyl, tridecoxyethyl, tetradeooxypropyl, pentadecoxypentyl, hexadecoxybutyl, heptadecoxyethyl, octadecoxyethyl, octadecoxyhexyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl, ethylaminoethyl, propyliaminoethyl, butylaininopropyl, ootylaminohexyl, hexylaminooctyl, heptylaminopentyl, octylaminooctyl, nonylaminoethyl, ethylaminononyl, decylaminopropyl, propylaminododecyl, idodecylaminoethyl, dodecylaminobutyl, dodecylaminohexyl, N-methyl N ethylaminoethyl, N-

propyl-N-ethylaminoethyl, N butyl-N-pentylaminoethyl, N-octyl-N-heXyl-arninobutyl, and N-decyl-Nbutylaminobutyl.

The compounds of this invention are prepared by reacting a ketonitrile having the formula R -C-(!7HC R the formula R NH is employed, and in which R =R,

then the reaction is conducted with a molecular ratio of substantially one of the ketonitrile to two of the amine. If it is desired to make the compound of Formula B, in which R and R represent diiierent embodiments, there is reacted on a substantially equimolecular basis, the ketonitrile of Formula F with the compound RNH to form an iminopyrroline. This iminopyrroline is then reacted in a substantially equimolecular way with the compound R NH in which R may represent any of its other aforementioned embodiments, except hydrogen.

The NH group in the reactants RNH and R NH must be attached to a hydrogen atom or to a carbon atom that is in turn attached to no more than two other carbon atoms. Otherwise, steric hindrance is observed and the reaction is not consummated.

The compound E is formed in appreciable amounts Whenever R represents an alkyl group of 1 to carbon atoms. In other Words, the R CH group in product E comes from the R when that symbol represents an alkyl group. i

The preferred structures are those of Formula B and D when R equals hydrogen and the remainder of the R symbols is alkyl. Also preferred are the compounds of Formula E when R is hydrogen or alkyl and the remainder of the R symbols is alkyl.

Typical ketonitrile reactants include 7 4-oxopentanonitrile, 3-methyl-4-oxopentanonitrile,

2,2-dimethyl-4-oxopentanonitrile, Z-methyl-2-ethyl-4-o;-;opentanonitrile, 2,4,8-trimethyl-4-cyano-d-nonanone, 7-methyl-7-cyano-9-pentadecanone, 2-methyl-2-propyl-4-oxoheptanonitrile, Z-methyl-Z-(2,2,4,4-tetramethylpentyl) 4-oxopentanonitrile, 2-rnethyl-2-ethyl-4-oxoheptanonitrile, Z-methyl-Z-hexyl-4-oxodecanonitrile, Z-isobutyl-Z,6-dirnethyl-4-oxoheptanonitrile, Z-rnethyl-Z-neopentyl-4-oxopentanonitrile, 2-methyl-2,4-diphenyl-4-oxobutanonitrile, 2-(1-cyanocyclohexyl)-cyclol1exanone, 2-rnethyl-2,4-dicyclohexyl-4-oxobutanonitrile, 5-'nethyl-2-( l-methyl-l-cyanoethyl) cyclohexanone, 1,3 ,3 -trimethyl-5-oxocyclohexanecarbonitrile, Z-acetyl-1-methylcyclopentanecarbonitrile, 1-butyl-2-methyl-3-oxocyclopentanecarbonitrile, 1- Z-oxocyclopentyl) cyclohexanecarbonitrile, l-( l-pentyl-Z-oxooctyl)cyclopentanecarbonitrile, 1-octyl-2-methyl-3 -oxocyclohexanecarbonitrile, 3 ,3 dimethyl 2-(2-oxopropyl) -bicyclo [2.2.1]heptane-2- carbonitrile, Z-benzoyl-l -rnethylcyclopentanecarbonitrile, and 2-butyl-2-naphthyl-4-oxobutanonitrile.

Typical iminopyrroline and irninopyrrolidine compounds of the Formulas B and E, wherein R equals hydrogen, which may be employed in order to form products of the same formulas, where R represents its other embodiments, include 2-methyl-5-dodecylimino-2-pyrroline, 2,4,4-trimethyl-5-octadecylimino-2-pyrroline, 2,4-dicycloheXyl-4-methyl-5-octadecylimino-Z-pyrroline, S-methylimino-Z,4,4-trimethyl-2-pyrroline, S-butylimino-Z,4,4-trimethyl-2-pyrroline, 2,4,4-trimethyl-5-butylirnino-l-pyrroline, 5-0enzylimino-2,4,4-trimethyl-2-pyrroline, 5 3 -rnethoxypropylimino -2,4,4-trimethyll -pyrroline, 2,4-dimethyl-4-neopentyl-5-(3 dirnethylaminopropylimino) -2-pyrroline, 4-ethyl-4-methyl-2-propyl-5-(Z-methyl-Z hydroxypropylimino) -2-pyrroline,- 2,4,4-trimethyl-5-phenylimin0-2-pyrroline, 2,4,4-trimethyl-5-p-tolylimino-2-pyrroline, l-dodecyl-2-imino-5-methylenepyrrolidine, 3-cyclohexyl-3-methyl-2-octadecylimino 5 cyclohexylidenepyrrolidine, l-butyl-2-irnino-3 ,3 -dimethyl-5-octylidenepyrrolidine, 3,3-dimethyl-2-imino-l-octadecyl-S-methylenepyrrolidine, 2,(3-dimethylaminopropylimino)-3-methyl3 neopentyl- S-butylidenepyrrolidine, 3,3-dimethyl-l-dodecyl-Z-ituino-S methylenepyrrolidine,

and 3,3-dirnethyl-2-imino-l-octyl-S-methylenepyrrolidine.

Illustrative reactants having the formula RNI-I are ammonia, methylamine, butenylarnine, aniline, naphthylarnine, benzylamine, ethylaniline, hexadecylaniline, ethylbenzylamine, dodecylphen v'lpropylamine, ethoxybutylamine, ethanolamine, and 'y-dimethylaminopropylamine. It should be noted that while the reactant RNH may possess more than one amino group it can have only one primary amino group for the purposes of this invention. Also, for the purposes of this invention, ammonia is equivalent to the defined primary monoamines having 7 the formula RNH Illustrative reactants having the formula R NH are methylamine, butenylamine, aniline, naphthylamine, benzylamine, p-ethylaniline, p-hexadecylaniline, ethylbenzylamine, dodecylphenylpropylarnine, ethoxybutylamine, ethanolamine, and v-dirnethylaminopropylamine. It should be noted that while the reactant R NH may possess more than one amino group, it can have only one primary amino group for the purposes of this invention.

The products corresponding to Formula A are predominantly formed when the reactants of this invention are mixed in substantially equirnolecular ratios at room temperatures or at temperatures up to about 75 C. and allowed to stand for prolonged periods of time. The For mula A products are generally crystalline solids which, when heated to a range approaching that required for distillation, lose water and are converted to a Formula B or E product.

The Formula 13 and E compounds, and these, of course, encompass types C and D as discussed heretofore, are predominantly produced when the reaction is conducted under conditions whereby water is removed. The preferred method is to conduct the reaction in the presence of an inert volatile organic solvent that forms an azeotrope with water. Useful as solvents in this respect are benzene, toluene, Xylene, heptane, hexane, methylene chloride, chloroform, and the like. If the RNH reactant is insoluble in water, an excess of that reactant may be employed as the solvent. The water is removed azeotropically as the reaction progresses, preferably at about 40 to 250 C., and very little, if any, of type A product is formed. The reaction is desirably terminated when the substantially theoretical amount of Water is removed. The product may be isolated by distillation under reduced pressure or recrystallization from a solvent, such as isooctane, as desired. If the RNH reactant has been used in excess to permit it to serve also as a solvent, it

has to be separated from the Formula B and E products at the conclusion of the reaction, by conventional methods, for reasons to be apparent hereinafter. It is possible in some instances to obtain mixtures of products, but this is no deterrent to the present invention.

If it is desired to form a compound from the Formulas and E, wherein R is other than hydrogen, from the corresponding compounds where R is hydrogen, this may be done by reaction of the B and E compounds, wherein R equals hydrogen with R NH in which R is other than hydrogen. The reaction is conducted with the evolution of ammonia. Generally, it is advisable to employ the amine reactant in excess or" the amount required in order to assure completeness of reaction and maximum yields. The reaction temperature ranges from about 75 to 300 C., preferably 100 to 200 C. A temperature is conveniently employed at which ammonia is liberated, and the reaction is continued until an equivalent of ammonia is liberated. The reaction is preferably conducted in the presence of an inert volatile organic solvent, such as benzene, toluene, xylene, heptane, hexane, methylene chloride, chloroform, and the like. It is also possible to employ as solvent the R NH reactant in an amount in excess of that required for its reaction. The product may be isolated by distillation under reduced pressure or recrystallization from a solvent, such as isooctane, as desired. it the amine reactant has been used in excess to permit it to serve also as a solvent, it may be readily separated from the product at the conclusion of the reaction by conventional methods.

The products or" this invention, whether of the Formulas A, B, or E, or mixtures thereof, are useful as fungicides, aphicides, and miticides. These compounds are particularly ei'fective against Stemphyiium sarcinaeforme and A Ionz'linia fructicola in concentrations as low as 0.005% to 0.01% and lower when applied and evaluated according to standard methods. Fungicidal activity of the present compounds generally increases as the molecular weight increases, especially in the range of 250 to 650, wherein many of the compounds of this invention are effective against Stemphylizlm sarcinaeforme and Monz'linz'a fruczicola in concentrations as low as about 1 to 16 parts per million. The compounds of this invention have high aphicida-l and miticidal activity, particularly those of Formulas A, B, and E, wherein R represents hydrogen, many of which are effective at concentrations of about 75 to 100 parts per million. Particularly effective as pesticides are S-dodecylimino-2,4,4-trimethyl-2-pyrroline, 5-octadecylimino-2,4,4-trimethyl-2-pyrroline, l-dodecyl-S-dodecyliminc-2,4,4-trimethyl-2-pyrroline, l-benzyl-S-benzylimino-4-methyl-2,4-bis Z-rnethylpropyl -2-pyrroline, 1-butyl-5-benzylimino-2,4,4-trimethyl-2-pyrroline, ldodecyl-5-dodecylimino-2,4-bis (Z-methylpropyl) -4- methyl-Z-pyrr oline, l-octadecyl-S-octadecyliminc-2,4,4-trimethyl-2-pyrroline, l-phenyl-S -phenylimin-2,4,4-trimethyl-2-pyrroline, l- 2-hydroxyethyl) Z-hydroxyethylimino) -2,4,4-trimethyl-Z-pyrroline, 1-butyl-5-butylimino-Z,4,4-trimethyl-2-pyrroline, l-benzyl-5 -butylimino-2,4,4trimethyL2-pyrroline, 2-dodecylimino-2,4,4-trimethyll -pyrroline, 3 ,3-dimethyll-hexade cyl-Z-imino-5-methylenepyrrolidine, 1-dodecyl-5-imino-2,4,4-trimethyl-2-pyrroline, 3 ,3-dimethyl-l dodecyl-2-imino-5-methylenepyrrolidine, 3 ,3 -dimethyll -o ctyl-Z-octylirnino-S -methylenepyr-rolidine, l-dode cyl-Z-do decylirnino-3 3 -dimethyl-5-methylenepy-rrolidine, and 1-benzyl-2-benzylimino-3 -methyl-3 Z-methylpropyl) -5- (Z-methylpropylidene -pyrrolidine.

The compounds of this invention have been presented in their free-base form and in this free-base form, they possess the valuable characteristics and concurrent utili ties previously referred to. However, it is to be construed that the present invention includes the acid addition salts of these free-base products also. It is desirable, in some instances, to employ the present products in their Water-soluble salt form. For instance, in pesticidal applications, it is highly desirable to deal with Water-soluble compounds in order that satisfactory spray solutions may be formulated. In other applications, wherein any physiological benefits are desired, it is frequently advantageous to employ the present products in their organic salt form in order to provide substantial neutrality with stability.

In order to prepare the salt forms of the present compounds, it is necessary only to react these compounds With a stoichiometric amount of the selected acid. The salt formation occurs readily at room temperature without the aid of a catalyst. If solid reactants are employed, it may be advantageous to use an inert volatile solvent such as benzene, toluene, xylene, hexane, heptane, methylene chloride, chloroform, or the like. The solvent can then be readily removed at the conclusion of the reaction by conventional methods. The salt product does not require any further purification although recrystallization from a solvent such as isooctane may be resorted to if a product of high purity is demanded.

While it is believed clear to one skilled in the art from the above description how the salts are prepared, such salt formation may be specifically illustrated by indicating that one would take an equivalent amount of a selected compound of this invention in its free-base form and then add a stoichiometric amount of a selected acid which would, for instance, be 36.5 parts of hydrochloric acid, 98 parts of sulfuric acid, 60 parts of acetic acid, 72 parts of acrylic acid, and the like. The corresponding hydrochloric, sulfuric, acetic and acrylic acid salts respectively are readily formed. Similarly, other salt products may be prepared.

Typical organic and inorganic acids that may be employed are formic acid, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, undecylenic acid, oleic acid, linoleic acid,

, linolenic acid, ricinoleic acid, propiolic acid, butynoic acid, cyclobutanecarboxylic acid, norcamphanc-Z-carboxylic acid, benzoic acid, resorcylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, salicylic acid, maleic acid, fumaric acid, glutaconic acid, saccharic acid, dodecanedioic acid, octendioic acid, cyclohexaneacetic acid, cyclopentaneacetic acid, tridecanoic acid, hexynedioic acid, phthalic acid, cinnamic acid, benzenesulfonic acid, ethanesulfonic acid, naphthalenesulfonic acid, toluenesulfinic acid, glutamic acid, glyoxalic acid, phenylglyoxalic acid, pyruvic acid, levulinic acid, glycine, aminocaproic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, perchloric acid, carbonic acid, nitric acid, and phosphoric acid.

The compounds of this invention, as well as the methods for their preparation, may be more fully understood from the following examples which are ofiered by Way of illustration and not by way of limitation. Parts by weight are used throughout.

EXAMPLE 1 Redistilled laurylamine parts), 2,2-dimethyl-4- oxopentanonitrile (95 parts), and toluene (40 parts) are placed in a reactor fitted with a Water separator and a reflux condenser. The material is heated to reflux and water (13 parts) is removed during the ensuing one hour period. The pot temperature rises from 132 to C. during the reflux period. The reaction mixture is then distilled under reduced pressure. The product boils at 146149 C. (0.4 mm. absolute pressure) success and solidifies in the receiver. 92% of the theoretical.

Calculated for C H N Nitrogen, 9.6%.

trogen, 9.4%.

The yield is 201 parts,

Found: Ni-

Recrystallization of the solid product from heptane solution gives a pure solid, M.P. 92.092.5 C. At least 70% of the product is obtained as this crystalline modification. The combined filtrates afrom such separations are redist-illed to give a liquid product which,

on the basis of spectroscopic data, is believed to be primarily the isomer corresponding to Formula E.

Attempted nitrosat-ion of the solid tautomer with sodium nitrite and hydrochloric acid gives only recovered starting material. When the liquid product is treated in the same manner, isomerization to the solid product occurs.

EXAMPLE 2 EXAMPLE 3 Octadecylamine (135 parts), 2,2-dimethyl-4-oxopentanonitrile (65 parts) and toluene (150 parts) are combined in a flask fitted with a water separator and a reflux condenser. The mixture is boiled under reflux for forty-five minutes during which time the theoretical amount of Water (8 parts) separates. The reaction mixture is stripped under reduced pressure and distilled to give the product "(117 parts), B.P. 183-199 C. (0.2 absolute pressure).

Calculated (for cz5H4gN2:

Nitrogen, 7.30%.

The product solidifies on cooling to room temperature in the receiver. t is identified as 2,4,4-trimethyl-5-octa- Nitrogen, 7.44% Found:

decylimino-Z-pyrroline and 3,3-dirnethyl-2-imino-l-octadecyl-S-methylenepyrroldine.

In a similar manner, 3amethyl-4-oxopentanonitrile is converted to 2,3-dimethyl-5-octadecylimino-Z-pyrroline, 2,3'-dimethyl-5-octadecylimino-l-pyrroline, and 1-octadecyl-2-imino-rnethyl S-methylenepyrrolidine; Z-methyl- 2,4-dlCYCll1CXY1-4-OXO'blltfiIlOflillllG is converted to 4- methyl-Z,4-dicycloheXyl--octadecylimino-Z-pyrroline, 3- cyc'lohexyl 2 imino 3 methyl 1 octadecyl 5- cyclohexylidenepyrrolidine, and 5 octadecylimino 4- methyl-2,4-dicyclohexyl-1-pyrroline; and S-methyl-Z-(lmethyl-l-cyanoethyl)cyclohexanone is converted to 2- octadecylimino 3,3,6 trimethyl 2,3,4,5,6,7 hexahydroindole and 2-imino-1-octadecyl-3,3,6-trimethyl-2,3,4,5, 6,7-hexahydroindole.

EXAMPLE 4 Cyclohexylam ine (198 parts), 2,2-dimethyl-4-oxopentanonitrile (125 parts), and benzene (50 parts) are heated at reflux for five hours to azeotrope out water as formed. The reaction mixture is then fractionated under reduced pressure and the product, B.P. 10l-103 8 C. (0.6 mm. absolute pressure), is obtained in a yield of 93% of the theoretical.

Calculated for C H N Nitrogen, 13.6%; neutral equivalent, 206. Found: Nitrogen, 13.4%; neutral equivalent, 207.

The product crystallizes on standing.

EXAMPLE 5 Anhydrous monomethylamine (74 parts) and 2,2- dirnethyl-.-oxopentanonitrile (63 parts) are charged to an autoclave and allowed to stand under autogenous pressure for seventy-two hours. The autoclave is vented and the autoclave contents are heated to 125 C. to expel the last of the methylarnine. The residue is transferred to a distillation flask and distilled under reduced pressure. The product is collected in the range of 77 -9l C. (14 mm. absolute pressure) and has n 1.5069.

Calculated for C H N Nitrogen, 20.3%; neutral equivalent, 138. Found: Nitrogen, 19.7%; neutral equivalent, 142. a

These results show that the product is 2,4,4-trirnethy1-5- methylimino-2-pyrroline and 1-methyl-2-imino-3,3-dimethyl-5-methylenepyrrolidine.

EXAMPLE 6 Butylamine (73 parts) and 2,2-dimethyl-4-oxopentanonitrile (63 parts) are heated at reflux for one hour. The reaction mixture is then stripped under reduced pressure and distilled to give the product 2,4,4-trimethyl-5- butylimino-Z-pymroline and 1-butyl-2-imino-3,3-dimethyl- S-methylenepyrrolidine in 78% yield, B.P. 80-90 C. (4.8 mm. absolute pressure). The product corresponds to the formulas:

CH3 ctr-i and EXAMPLE 7 Benzylamine (27 parts), 2,2-dimethyl-4-oxopentanonitrile (31 parts), and toluene (20 parts) are refluxed and Water is removed azeotropical ly. When the Water ceases distilling, the mixture is distilled under reduced pressure. The product, 2,4,4-trimethyl-5-benzylimino-2- pyrroline and 1-benzyl-2-imino-3,3-dimethyl-5-methylenepyrrolidine, has a B.P. 114 C. (0.4 mm. absolute pressure), M.P. 97.599 C. on recrystallization from ether.

Calculatedfor C H N Nitrogen, 13.1%.

Nitrogen, 12.9%.

The product darkened in air on standing.

In a similar manner, 2,2-dirnethyl-4-oxopentanonitrile reacts with 3-methoxypropylamine to give 2,4,4-trimethyl- 5-(3-rnethoxypropylimin0)-2-pyrroline and 1-(3-methoxypropyl-Z-imino)-3,3-dimethyl-S-methylenepyrrolidine, 2- methyl-Z-neopentyl-4-oxopentanonitrile reacts with 3-diethylaminopropylamine to give 2,4-dimethyl-4-neopenty1- 5-(3-diethylarninopropylimino)-2-pyrroline and 1-(3-diethylaminopropyl) 2 imino 3 methyl 3 neopentyl- S-methylenepyrrolidine, and '2-methyl-2-ethyl-4-oxoheptanonitrile reacts with Z-hydroxy-Z-methylpropylamine to give 4-methyl-4-ethyl-Z-propyl-S-(Z-methyl-Z-hydroxypro- Found:

pylimino)-2-pyrroline and 1-(2-methyl-2-hydroxypropyl) Z-imino-3-methyl-3-ethyl-S-propylidenepyrrolidine.

EXAMPLE 8 Aniline (116 parts), 2,2-dimethyl-4-oxopentanonitrile (125 parts), artiline hydrochloride (5 parts), and toluene (40 parts) are combined and refluxed under a water separator. When the theoretical amount of water (18 parts) has been removed, the reaction mixture is distilled under reduced pressure. The product, 2,4,4-trimethyl-5-phenylimino-Z-pyrroline and 1-phenyl-2-imino-3,3-dimethyl-5- methylenepyrrolidine, has B.P. 102l07 C. (0.3 mm. absolute pressure).

Calculated for C H N Nitrogen, 14.0%. Found: Ni-

trogen, 13.8%.

In a similar manner, 2,2-dimethyl-4-oxopentanonitrile and p-toluidine give 2,4,4-trimethyl-S-p-tolylimino-2-pyrroline and 2-p-tolylimino-3,3-dimethyl-5-rnethylenepyrro lidine and 2-(l-cyanocyclohexyl)-cyclohexanone and anapnthylamine give 2-iz-naphthylimino-3,3-pentamethylene-2,3,4,5,6,7-hexahydroindole.

EXAMPLE 9 The mixture of benzylamine (26.8 parts) and 2,2-dimethyl-4-oxopentanonitnile (31.2 parts) is allowed to stand in a stoppered flask for one month. The solid product which forms is separated by filtration and is recrystallized from acetone to give the product 2,4,4-trimethyl- 2 hydroxy-S-benzyliminopyrrolidine (36 parts), M.P. 119.5 123 C. A second crystallization gives the analytical sample, M.P. 127 C.

Calculated for C A-1 14 0: Carbon, 72.4%; hydrogen,

8.7%; nitrogen, 12.1%; hydroxyl number, 241; molecular Weight, 232. Found: Carbon, 72.6%; hydrogen, 9.0%; nitrogen, 11.9%; hydroxyl number, 250; molecular Weight, 243.

These data together with spectroscopic data establish the structure of the product.

EXAMPLE A mixture of 2,2-dimethyl-4-oxopentanonitrile (25 parts) and anhydrous methylamine (31 parts) is allowed to stand at 0 C. for six hours and at room temperature for seventy-two hours. A solid separates from the reaction mixture. The crude product, M.P. 108-1l1.5 C. is recrystallized from heptane to give the purified product, 2-hydroxy-2,4,4-trimethyl-S-methylirninopyrrolidine, M.P. 120123 C.

Calculated for C H N O: Nitrogen, 17.9%; neutral equivalent, 156. Found: Nitrogen, 17.9%; neutral equivalent, 156.

In asimilar fashion, allylamine and 2-(1-cyanocyclo hexyl)-cyclohexanone give 2-allylimino-3,S-pentamethylene-7a-hydroxy-2,3,3a,4,5,6,7,7a-octahydroindole, and 2- ethoxyethylamine and 5-methyl-2-(l-methyl-l-cyanoethyl) cyclohexanone give 2-(2-ethoxyethylimino)-7a-hydroxy-3,3,6-trimethyl-2,3,3a,4,5,6,7,7a-octahydroindole.

EXAMPLE 11 Benzylamine (214 parts), 2,2-dimethyl-4-oxopentanonitrile (63 parts), and toluene (400 parts), are combined in a reactor fitted with a water separator and a reflux condenser. The vent from the condenser is connected to a gas scrubber. A stream of nitrogen is swept through the reactor and condenser system to purge gases through the scrubber. The scrubber is filled with standardized acid solution. The reaction mixture is boiled under reflux and a record kept of the time, pot temperature, parts of water removed, and change in concentration of the standardized acid solution in the scrubber.

Pot Temp. Aqueous Ml. NaOH Time (hours) in C. Distillate, (.1 N)/cc. ml. H01 soln.

Inspection of the table shows that all of the water has separated before any significant amount of ammonia is evolved. Thus, the formation of 5-benzylimino 2,4,4-tri methyl-Z-pyrroline and 1benzyl-2-imino-3,3-dimethyl-5- methylenepyrrolidine, goes to completion before significant displacement of ammonia occurs. The reaction mixture is distilled under reduced pressure. The product, 1- benzyl-S-benzylimino-2,4,4-trimethyl-2-pyrroline and 1- benzyl 2-benZylimino-3,3-dimethyl-S-methylenepyrrolidine, (131 parts), has a boiling point of 167170 C. at 0.1 mm. absolute pressure and an 11 value of 1.5841. The product contains 9.2% nitrogen (theoretical 9.2%).

Following the same procedure, benzylamine and 3- methyl-4-oxopentanonitrile give l-benzyl-S-benzylimino- 2,3-dimethyl-2-pyrroline and 1-benzy1-2-benzylimino-4- methyl-S-methylenepyrrolidine; benzylanfine and Z-m'ethyl-Z-hexyl-4-oxodecanonitrile give l-benzyl-S-benzylimino-2,4-dihexyl-4-methyl-2-pyrroline and 1-benzyl-2-benzylirnino-3 hexyl-3-methyl-5-hexylidenepyrrolidine; benzylamine and 2,6-dirnethyl-2-(2-methylpropyl)-4-oxoheptanonitrile give 1-benzyl-5-benzylimino-2,4-bis(Z-methylpropyl)-4 methyl-2-pyrroline and l-benzyl-Z-benzylimino- 3-metliyl-3-(2-methylpropyl) 5 (2-methylpropylidene)- pyrrolidine; and benzylamine and 2-methyl-2-(2,2-dirnethylpropyl)-4-oxopcntanonitrile give 1-benzy1-5-benzylimino-2,4-dimethyl-4-(2,2-di-methylpropyl)-2-pyrroline and 1- benzyl-2-benzylimino-3 methyl 3 (2,2-dimethylpropyl)- S-methylenepyrrolidine.

EXAMPLE 12 A mixture of 2,2-dimethyl-4-oxopentanonitrile (303 parts), butylamine (234 parts), and hexane (150 parts by volume) is boiled under reflux in a reaction fitted with a water separator and reflux condenser. After five hours, the theoretical amount of Water has separated. The reaction mixture is stripped of hexane and excess butylamine to a pot temperature of C. at 30 mm. absolute pressure. To the residue is added butylamine (365 parts) and the mixture is charged to an autoclave md heated to 200 C. From time to time, ammonia is vented from the unit. The total time required is about 20 hours. The product, 1-butyl-5-butylimino2,4,4-trirnethyl-2-pyrroline and 1-butyl-2-butylimino-3,3-dimethyl-5-methylenepyrrolidine, (425 parts) has a boiling point of 93 96 C. at 0.1 mm. absolute pressure and an n value of 1.4850. The product contains 11.6% nitrogen (11.9% theoretical) and has a neutral equivalent of 235 (236 theoretical) In the same manner, 2-acetylcyclohexanecarbonitrile gives 1-butylimino-2-butyl-3-methyl-1,4,5,6,7,7a-hexahydroisoindole; 3,3-dimethyl-2-(2-oxopropyl)-bicyclo(2.2.1) heptane-Z-carbonitrile gives spiro{3,3-dimethylbicyclo (2.2.1)heptane 2,4 [1'-butyl-2'-rnethyl-5'-butylirnino- 2'-pyrr0line]}; and a,u,4-trirnethyl-2-oxocyclohexanacetonitrile gives 1-butyl-2-butylimino-3,3,6atrimethy1-2,3,4,5, 6,7-hexahydroindole.

EXAMPLE 13 A mixture of 2,2-dimethyl-4-oxopentanonitrile (94 parts), dodecylamine (280 parts), and toluene (70 parts) is boiled under reflux in a reactor fitted with a water separator and reflux condenser. The vent of the condenser is led to a scrubber filled with standard acid in order to follow the evolution of ammonia. The mixture reaches 188 C. in the pot within 40 minutes after boil-. ing begins. At that point, the theoretical amount of water (14.5 parts) has separated. In the course of 49 hours of boiling, the temperature reaches 248 C. and very nearly the theoretical amount of ammonia has been evolved. The product is distilled under reduced pressure. The product is isolated at 219-224 C. at 0.3 mm. absolute pressure. The product has an 77 value of 1.4780, has a neutral equivalent of 456 (460 theoretical), and contains 6.10% nitrogen (6.08% theoretical). The product is identified as 1-clodecyl-5-dodecylirnino-2,4,4- trimethyl-Z-pyrroline and 1-dodecyl-2-dodecylimino3,3- dimethyl-S-methylenepyrrolidine.

Following the procedure of Example 13, the following materials are prepared. Table I gives the physical prop- 12 imino-2,4,4-trimethyl-2 pyrroline (90 parts) in a reactor fitted With a vent which leads to a scrubber containing standard acid solution. The theoretical amount of ammonia is evolved in the course of 55 hours. Fractionation of the residue gives a out having a boiling point of 150167 C. at 2 mm. absolute pressure and has an n value of 1.5388. The product contains 10.4% nitrogen (10.4% calculated) and has a neutral equivalent of 271 (270 theoretical). From the foreruns of this experiment are obtained a small amount of l-butyl-S-butylimino-2,4,4-trimethyl-Z-pyrroline and l-butyl-Z-butylimi- 110-3,3-dimethyl-S-rnethylenepyrrolidine and in a highboiling cut, a slightly larger amount of l-benzyl-S-benzylimino-Z,4,4-trimethyl-2-pyrroline and l-benzyl-Z-benzylirnino-3,3-dimethyl-S-methylenepyrrolidine is also isolated.

B. Butylamine (72 parts) and 5-benzylimino-2,2,4-trimethyl-Z-pyrroline (108 parts) are boiled under reflux for 100 hours. In the course of this heating period some erties of the products so prepared. loss of butylamine occurs; make-up butylamine is added Table I from time to time to keep the original volume constant.

CH The product is obtained which boils in the range of 92- 3 124 C. at 2 mm. absolute pressure and has an 71 value -R5 of 1.5 360-15393. The neutralization equivalents and the I 25 nitrogen contents for each of the three sub-cuts within N/ this range all check well with the theoretical values R (10.4% nitrogen and 270 neutral equivalent). Again, 1- and butyl 5 butylimino 2,4,4 trimethyl 2 pyrroline CH3 and l-butyl 2 butylimino 3,3 dimethyl 5 methylenepyn'olidine are isolated from the foreruns and 1- *T benzyl 5 benzylimino 2,4,4 trimethyl 2 pyrroline R6CH and 1-benzyl-2-benzylimino-3,3-dimethyl-5-methylenepyr- T rolidine are isolated from the residue. The infrared ab- R5 sorption spectra of the cuts from this run and from part Boiling Percent Molec- Point Melting nitrogen R R=R R =R ular 0.1mm. Point 11,,

Weight absolute C.) 7

pressure) Cale. Found H 11 0.8113 CH3 s20 290-300/05 4.45 4.47 H 05H; on; 27s 173-174/45 10.1 11.3 H ongomonfi CH3 212 134-141 0. 15 106-108 13.2 13.2

CH2CHCH=.- CsH5CH2. CH2(|3HCH3 388 1s4-191/a5 1. 5520 7.21 7,16

CH3 CH3 CHz(!JHCH= 0121325 CHz(|JHCHa 545 245-25s/1.3 1. 4779 5.14 5.10 I

CH3 CH3 In the same manner, 1-(2-oxocyclohexyl)-1-cyclohexanecarbonitrile gives 1-p-tolyl-2-p-tolylimino-3,3-pentamethylene-2,3,4,5,6,7-hexahydroindole when reacted with p-tolylamine; 1- (2butoxyethyl) -2- Z-butoxyethylimino) 3,3-pentamethylene-2,3,4,5,6,7-hexahydroindole when reacted with Z-butoxyethylamine; and1-(3-dimethylaminopropyl) 2 (3-dimethylaminopropylimino) 3,3 pentamethylene-2,3,4,5,6,7-hexahydroindole when reacted with 3-dimethylarninopropylarnine.

Similarly, Z-methyl-Z-(2,2-dimethylpropyl)-4-oxopentanonitrile gives l-hexadecyl 5 hexadecylimino-2,4-dimethyl-4-(2,2-dimethylpropyl)-2-pyrroline and l-hexadecyl-2-hexadecylimino-3 -methyl-3 (2,2-dimethylpropyl) S-methylenepyrrolidine when reacted with hexadecylamine; 1-(2-ethylaminoethy1)- 5 '-(2-ethylaminoethylirnino) -2,4dimethyl-4- 2,2-dimethylpropyl) -2 -pyrroline and 1-(2-etl1ylaminoethyl) 2 (Z-ethylaminoethylimino)-3- methyl-3-(2,2-dimethylpropyl) 5 methylenepyrrolidine when reacted with Z-ethylaminoethylamine; and 1-(2- phenylethyl) 5 (Z-phenylethylimino)-2,4-dimethyl-4- (2,2-dimethylpropyl)-2-pyrroline and 1-(2-phenylethyl)- 2- (phenylethylimino)-3-rnethyl 3 (2,2-dimethylprop-y l)- S-methylenepyrrolidine when reacted with 2-phenylethy1- amine.

EXAMFLE 14 A. Benzylamine (214 parts) is heated with S-butyl- 2-butylimino-3,3-dimethyl-S-methylenepyrrolidine and 1- butyl-2-benzylin1ino-3,3-dimethyl-5-methylenepyrrolidine.

EXAMPLE 15 Mesitononitn'le '(600 parts, 4.8 moles), laurylamine (906 parts, 4.9 moles), and xylene (2 00 parts) are charged to a 3-liter one-necked flask which is fitted with a water separator and a condenser. The material is heated to boiling and a rapid reflux rate is maintained While the water separates. The pot temperature rises from 112 to 225 C. during the approximately 1% hour period which is required for separationof the water (84 parts, 4.7 moles). The cold reaction mixture is filtered to separate the solid isomer. Xylene is removed by stripping the filtrate =(1094 parts) at reduced pressure to a final weight of 99 8 parts. Additional liquid product (224 1.3 parts) is separated from the heptane solution used to wash the solid isomer. The total yield of crude liquid product (1318 parts, 4.17 moles) is 84.9% based on the mesitononitrile charged, and is identified as l-dodecyl- 2-imino-3,3-dimethyl-S-methyienepyrrolidine.

The solid isomer (211 parts, 0.72 mole) represents a yield of 15%.

In another run in which less xylene (50 parts) is used, the final reaction temperature is 292 C. This crude product is distilled to give a 46% yield of liquid isomer and 23% solid isomer.

This application is a continuation-impart of application Serial Nos. 718,591, 718,507, and 718,509, all filed March 3, 1958 all of which are now abandoned.

We claim:

1. The compound, a member selected from the group consisting of compounds having the formulas:

and

INCH: \N/ :NR

R and the acid addition salts thereof, in which R and R are each members selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and alkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 19 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, and R is a member selected from the class consisting of hydrogen and alkyl of 1 to '9 carbon atoms.

2. The compound of the formula in which R R and R are alkyl groups of 1 to 10 car- 14* bon atoms, R is an alkyl group of 1 to 18 carbon atoms, and R is a hydrogen atom.

3. The compound of the formula in which R R and R are alkyl groups of 1 to 10 carbon atoms, R and R are alkyl groups of 1 to 18 carbon atoms, and R is a hydrogen atom.

4. The compound of the formula in which R R and R are alkyl groups of 1 to 10 carbon atoms, R is an alkyl group of 1 to 18 carbon atoms, and R is a hydrogen atom.

8. The compound of claim 2 in which R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring free of aromatic unsaturation of 5 to 6 carbon atoms.

9. The compound of claim 3 in which R is hydrogen.

10. The compound of claim 3 in in which R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring free of aromatic unsaturation of 5 to 6 carbon atoms.

11. The com-pound 3,3-dimethyl-l-dodecyl-Z-imino-S- methylenepyrrolidine.

12. The compound 3,3-dimethyl-1-dodecyl-2-dodecy1- imino-5-methy1enepyrrolidine.

13. The compound 2-benzylimino-5-hydroxy-3,3,5-trime-thylpyrrolidine.

14. The compound 2,4,4-trimethyl-5-dodecylimino-2- pyrroline.

15. The compound 2,4,4-trimethyl-5-dodecylimino-1- pyrroline.

16. A method for the preparation of the compound having the formula which compnises reacting in substantially equimolecular proportions at a temperature of about 25 to 75 C., the formula RNH with a compound having the formula in which R is a member selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenyla-lkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxysnoasaa alkyl groups of 2 to 12 carbon atoms, and alkylarninoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, and R and R taken collectively with the carbon atoms, to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms.

17. A method for the preparation of the compound having the formula and removing the water for-med in the reaction, in which R is a member selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and alkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a :carbccyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, and R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl lsu 'bstituents of a total of no more than 4 additional carbon atoms.

18. A method for the preparation of the compound having the formula "16 which comprises reacting at a temperature of about 40 to 250 C., R NH with and removing the water formed in the reaction, in which R is a member selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alltylphenylalkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and alkylaminoalkyl groups of 3 to 118 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon "atoms, R and R taken individually represent members selected from the class consisting of alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R is a member selected from the group consisting of hydrogen and alkyl of one to nine carbon atoms, n is an integer of one to ten, R and R taken collectively with the carbon atoms to which they are joined form a carbocycl c ring of 5 to 6 carbon atoms free of aromatic unsatu-ration including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total or" no more than 4 additional carbon atoms.

19, A method for the preparation of the compound having the formula in which R and R are each members selected from the class consisting of alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, alk'oxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and alkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups :of no more than 10 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, and R and R taken collectively with the carbon atoms to which they are joined form a carbocyciic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total or" no more than 4 additional carbon atoms, which comprises first reacting at 40 to 250 C. with the removal of water, the compound having the formula with one having the formula RNH and then with one 17 having the formula R NH at a temperature of about 75 to 300 C. until substantially an equivalent of ammonia is liberated.

20. A method for the preparation of the compound having the formula CnlH2nl- \N/ NR in which R and R are each members selected from the class consisting of alkyl groups of l to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and mkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of l to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of alkyl, cycloalkyl,

with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, and n is an integer of 1 to 10, which comprises first reacting at to 250 C. with the removal of water, the compound having the formula Blicke July 4, 1950 Bortnick et a1. May 16, 1961 

1. THE COMPOUND, MEMBER SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FORMULAS:
 11. THE COMPOUND 3,3-CIMETHYL-4-DODECYL-2-IMINO-5METHYLENEPYRROLIDINE. 